Bars and Confectioneries Containing Cocoa Solids Having A High Cocoa Polyphenol Content and Sterol/Stanol Esters and Processes for Their Preparation

ABSTRACT

Processes are provided for preparing ready-to-eat health bars such as chocolate granola bars and chocolate confectioneries such as dark or milk chocolate chews. The bars and confectioneries contain sterol ester(s) and/or stanol esters and cocoa solids having a high cocoa procyanidin content. The cocoa solids are pretreated with the sterol/stanol ester(s) or other edible oils or fats during the preparation of the products to prevent the loss of cocoa procyanidins. Other particulate antioxidants can be pretreated with food grade fats and/or oils or emulsifiers such as lecithin to conserve their effectiveness.

This application is a division of Ser. No. 10/672,232 filed Sep. 25,2003 now U.S. Pat. No. 7,329,429 issued Feb. 12, 2008.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The inventions relates to foods, food supplements, and or nutriceuticalscontaining sterol and/or stanol esters and cocoa polyphenols andprocesses for producing same. The products prepared by the processes ofthis invention have conserved levels of polyphenols.

2. Background of the Invention

Polyphenolic compounds are bioactive substances that are derived fromplant materials and are closely associated with the sensory andnutritional quality of products derived from these plant materials.

Many plant polyphenols have antioxidant activity and numerous healthbenefits. Consumption of the cocoa polyphenols in cocoa productsprovides significant health benefits. Cocoa polyphenols have been shownto have beneficial effects on the processes believed to be involved inthe development of atherosclerosis and cardiovascular disease. Cocoapolyphenols inhibit LDL oxidation, enhance nitric oxide/nitric oxidesynthase (NO/NOS) activity, and inhibit cyclo-oxygenase (COX) andlipoxygenase (LOX) activity. These effects are reported in WO 97/36497published Oct. 9, 1997. Cocoa polyphenols can also be used to treat orprevent conditions which are known to be affected by the administrationof non-steroidal anti-inflammatory drugs, for example, aspirin.

Despite the benefits of cocoa polyphenols on a number of pathways andconditions associated with induction and progression of atherosclerosisand coronary heart disease (CHD), it has been found that these compoundsdo not have a noticeable cholesterol-lowering effect. Thus, improvedcompositions containing polyphenols in combination with at least onecholesterol-lowering agent such as sterols and/or stanols or theiresters have been prepared. The compositions have enhanced effects on thevascular health of a mammal, particularly a human, in comparison topreviously known compositions containing polyphenols orcholesterol-lowering agents. See U.S. Pat. No. 6,610,320 issued Aug. 26,2003 to H. H. Schmitz et al.

It is known that cocoa polphenols can be lost during the processing ofcocoa ingredients containing cocoa polyphenols (e.g., cocoa solids,chocolate liquor, cocoa nibs, and cocoa extracts) into food products.Cocoa polyphenol losses can be avoided by pretreating the carbohydrateand/or the milk ingredient(s) used in food products with an antioxidant,an emulsifier, a fat, and/or a flavorant prior to the addition of thecocoa ingredient(s). See U.S. Pat. No. 6,194,020 issued Feb. 27, 2001 toM. E. Myers et al.).

Foods and dietary supplements containing cocoa ingredients andcholesterol-lowering agents such as sterols and/or stanols or their havebeen prepared. See the '320 patent discussed above. The sterols/stanolsor their esters may be added to the food or dietary supplement simply bymixing the sterol, stanol, and/or esters into the other ingredients. Tofacilitate mixing, the sterols/stanols may be first dissolved in asolubilizing agent such as a fat, a vegetable oil, a monoglyceride,diglyceride, or triglyceride, and/or tocopherols or suspended oremulsified in carriers such as water, alcohol polyol, or other ediblecompound in which the sterols/stanols or esters are at least partiallysoluble, for example chocolate liquor. During the preparation of acholesterol-lowering dark chocolate, for example, the sterols/stanolsmay be added to the dry mix containing the sugar and the butter or lesspreferably they may be added to the melted chocolate. During thepreparation of a toffee chew the sugar and the cocoa powder werepre-blended and then mixed with the caramel. Free phytosterols (as inpulverized) were added to the sugar and cocoa mix. During thepreparation of granola bars the syrup blend was prepared by melting palmkernel oil at 45 and adding to the oil a mixture of corn syrup,glycerin, cocoa powder, brown sugar, salt, lecithin and propyl gallateand then blending in nuts or soy puffs and semi-sweet chocolate pieces.

SUMMARY OF THE INVENTION

Standard confectionery techniques for making bars and chews result inlosses of flavanols and antioxidants compared to the known amounts addedto the bars and chews.

Accordingly, it would be highly desirable to prepare food products andnutraceuticals containing sterol esters and/or stanol esters and cocoapolyphenols where the cocoa polyphenols are not lost during processinginto the final product, i.e., products where the cocoa polyphenolspresent initially in the cocoa ingredients are conserved.

In the embodiments herein, reference to high CP cocoa solids and cocoasolids having a high cocoa procyanidin content is not intended to belimited to the polyphenols (i.e., procyanidins) present in the cocoasolids but is intended to cover other particulate food-gradeantioxidants.

In one embodiment, a process is provided for conserving theeffectiveness of a particulate, food grade antioxidant or anantioxidant-containing particles by pretreating the antioxidant-or theantioxidant-containing particles, prior to formulation into a food or afood supplement, with about 9% to about 90% by weight of a food-gradeoil and/or a fat having a melting point below about 80° C., preferablyabout 60° to about 80° C., and optionally with up to about 5% by weightan emulsifier, the weights being based on the weight of the antioxidantor the antioxidant-containing particles. Alternatively, the antioxidantor the antioxidant-containing particles can be pretreated with about0.75% up to about 5% by weight, preferably about 0.05 to about 0.3%,more preferably about 0.1% to about 0.3% of a lecithin. The antioxidantor antioxidant-containing particles have particle sizes of about 1 toabout 150 microns.

The antioxidants can be selected from the group consisting of lecithin,butylated hydroxyanisole, butylated hydroxytoluene, tertiary butylatedhydroquinone, propyl gallate, a phenolic acid, a polyphenol, ascorbicacid, stannous chloride, a tocopherol, sulfur dioxide, dilaurylthiodipropionate, and mixtures thereof.

The oil and/or the fat is selected from the group consisting of cocoabutter, a polyol ester, a sterol ester, a stanol ester, a triglyceride,a fatty alcohol ester of a polycarboxylic acid, an esterifiedalkoxylated polyol, a glycerol ester, a vegetable oil, a partiallyhydrogenated vegetable oil, and mixtures thereof.

The optional emulsifiers for use with the fat and/or the oil areselected from the group consisting of lecithin, a mono- or diglyceride,an ethoxylated mono- or diglyceride, a phospholipid, an ester of amonoglyceride and acetic, lactic, citric, succinic, or tartaric acid, afatty acid ester of a polyglycerol, a sorbitol ester, a sucrose ester,propylene glycol, polyglycerol polyresorcinoleate, and mixtures thereof.The preferred emulsifier is lecithin.

When the antioxidant-containing particles are a mixture of cocoapolyphenols present in fully defatted or partially defatted cocoasolids, the particles are preferably pretreated with about 20% to about40% by weight of sterol ester(s) and/or stanol ester(s) and optionallyup to about 20% of a chocolate liquor and/or with up to about 5% of alecithin, preferably soy lecithin.

In a second embodiment, an additive for a food or a food supplement anda process for its preparation is provided. The additive comprisespretreated, partially or fully defatted cocoa solids having a high cocoaprocyanidin (CP) content. The cocoa solids are pretreated by mixing withabout 9% to about 90% by weight, based on the cocoa solids, of sterolester(s) and/or stanol ester(s) which are liquids at temperatures ofabout 80° C. or less, preferably at about 60° C. to about 80° C. Thecocoa solids after the pretreatment have a cocoa procyanidin content ofat least about 50 to about 75 milligrams of a procyanidins, preferablyabout 60 to about 75 milligrams, and more preferably about 75 to about80 milligrams per gram of defatted cocoa solids. Alternatively, theadditive can comprise high CP, partially or fully defatted cocoa solidspretreated by mixing with up to about 5%, preferably about 0.05% toabout 0.1%, and more preferably about 0.1% to about 0.3% by weight,based on the cocoa solids, of a lecithin.

In a third embodiment, a binder syrup and a process for its preparationare provided. The binder syrup comprises (i) a syrup and (ii) high CPcocoa solids pretreated with about 9 to about 90% by weight of afood-grade oil and/or a fat which is a liquid at 80° C. or less,preferably at about 60 to about 80° C., and optionally with up to about5% by weight of a lecithin and/or up to about 20% of a chocolate liquor,preferably about 0.5% to about 10%, and more preferably about 0.5% toabout 3% of the chocolate liquor. The binder syrup is liquid at about60° C. to 80° C. and solid at room temperature.

It is prepared by mixing at about 20° C. to 160° C., preferably about50° C. to about 120° C., more preferably about 80° C. to about 110° C.,the syrup with pretreated cocoa solids. The high CP cocoa solids afterthe pretreatment have a cocoa procyanidin content of at least about 50to 75, preferably 60 to 75, more preferably about 75 to 80 milligrams ofcocoa procyanidins per gram of cocoa solids. Pretreatment of the high CPcocoa solids conserves at least about 65% to 100% of the cocoaprocyanidin originally present in the cocoa solids.

In a fourth embodiment, a dry, ready-to-eat food and a process for itspreparation is provided. The process comprises the steps of: (a)pretreating high CP cocoa solids with about 9% to 90% of sterol ester(s)and/or stanol ester(s) and optionally with up to about 20%, preferablyabout 1.5-10%, and more preferably about 0.5-3% of a chocolate liquorand/or up to about 5% of an emulsifier; the weights being based on thecocoa solids; (b) mixing the pretreated cocoa solids and a syrup with amixture of dry ingredients comprising grain(s), flour(s), and/orprotein(s) and optionally dried fruits and/or nuts to obtain a formablefood; and (c) forming the food. The cocoa solids prior to thepretreatment have a cocoa procyanidin content of at least about 75milligrams per gram of defatted cocoa solids. The pretreated cocoasolids and the syrup are liquid when blended into the dry ingredientsand solid when the formed food is cooled to room temperature.Optionally, the food can be decorated or enrobed with a chocolate, ayogurt, or a flavored sugar. Preferably, when a granola bar is beingprepared, the pretreated cocoa solids and the syrup are premixed atabout 60° C. to about 80° C. to form a binder syrup prior to blendingwith the dry ingredients. The preferred cocoa solids are partiallydefatted cocoa solids containing about 8 to about 30% fat and having acocoa procyanidin content of at least about 50 to about 150 milligrams,preferably about 50 to about 80 milligrams. The preferred sterolester(s) are prepared from rapeseed oil and comprise β-sitosterol,campesterol, and stigmasterol. The emulsifier can be selected from thegroup discussed above; the preferred emulsifier is lecithin. Thepreferred syrup is a corn syrup having a DE of about 40 to about 65. Thesyrup optionally comprises a whole milk powder, a skim milk powder,and/or a malted milk powder, a flavorant, one or more vitamins and/orminerals, a sugar such as brown sugar and/or fructose, and/or a salt.The dry ingredients used for the granola bar include grains such as ricecrisps, soy crisps, and/or oats. Other useful dry ingredients are flourssuch as bran, corn, wheat, and/or rice flour and proteins such as a milkprotein, an egg protein, a soy protein and/or whey. A dry, ready to eatchocolate granola bar optionally containing almonds, dried cherries, orblueberries can be prepared by this process. The bar contains at leastabout 2, preferably about 2 to about 25, more preferably about 2.5 toabout 10, and most preferably about 3 to about 7 milligrams of cocoaprocyanidins per gram of the bar which is at least about 65%, typicallyabout 90 to 100%, of the cocoa procyanidin originally present in thecocoa solids used to prepare the bar. The bar also contains about 4 toabout 200, preferably about 40 to about 65 milligrams of sterol ester(s)and/or stanol ester(s) per gram of the bar.

In a fifth embodiment, a chocolate confectionery such as dark chocolateor milk chocolate chew and a process for their preparation are provided.The process comprises (a) pretreating cocoa solids having a cocoaprocyanidin content of at least about 5 milligrams per gram of defattedcocoa solids with about 9 to about 90% of sterol ester(s) and/or stanolester(s) and with up to about 20%, preferably about 0.5% to about 10%,and most preferably about 0.5% to about 3% of chocolate liquor and/orwith up to about 5%, preferably about 0.5% to about 5% of an emulsifier;(b) blending the pretreated cocoa solids with a syrup at about 20° C. toabout 160° C.; (c) cooling the blend to about 5° C. to about 60° C.,preferably about 15° C. to 40° C., and more preferably 20° C. to about30° C. and (d) shaping the cooled blend into the confectionery. Thepreferred cocoa solids have a fat content of about 8% to about 30%, morepreferably 10-12% and a cocoa procyanidin content of about 50 to about150 milligrams. The preferred sterol esters are prepared from rapeseedoil and comprise esters of β-sitoserol, campesterol, and stigmasterol.The emulsifiers discussed above can be used; the preferred emulsifier islecithin. When chocolate liquor and/or lecithin are used, they arepreferably premixed with the sterol ester(s) and/or stanol ester(s)before addition to the cocoa solids. The syrup is an aqueous solution ofa nutritional carbohydrate sweetener or artificial sweetener. The syruphas a moisture content of about 1% to about 15%. The syrup may furthercomprise a gum, vitamin(s) and/or mineral(s), a sugar such as brownsugar and/or fructose, and/or a flavorant. The preferred syrup is one ormore corn syrups having a DE of about 40 to about 65. The dark or milkchocolate chews thus prepared contain at least about 2, preferably about2 to about 25, more preferably about 2.5 to about 10, and mostpreferably about 3 to about 7 milligrams of cocoa procyanidins per gramof chew and about 4 to about 200 milligrams, or typically about 40 toabout 65 milligrams of sterol esters per gram of the chew. The chewscontain about 65 to 100%, typically about 90-100%, of the cocoaprocyanidins originally present in the cocoa solids.

The pretreated high CP cocoa powders of the present invention are usefulin foods and food supplements other than those exemplified herein. Forexample, they are useful in the preparation of chocolate confectioneriesincluding SOI and non-SOI chocolates particularly semi-sweet and darkchocolates, cookies including brownies, cakes, chocolate coatings,toffees, caramels, hard candies, and the like.

Chocolate snacks prepared by the above processes improve or promotevascular heart health in a mammal. These ready-to-eat snacks containflavanols, specifically cocoa procyanidins, that promote healthycirculation and healthy blood vessels. They contain heart healthyvitamins such as B6, B12, and folic acid as well as antioxidant vitaminsE and C and/or calcium. In addition, they contain plant sterol and/orstanol esters that are proven to reduce bad cholesterol (LDL) by up toabout 15%. For maximum benefit, the snacks should be used as part of adiet that is low in saturated fat and cholesterol.

DESCRIPTION OF THE DRAWING

The FIGURE is a flow chart showing the preparation of a chew from apretreated antioxidant or antioxidant-containing particle and a syrupand the preparation of a food bar from a pretreated antioxidant orantioxidant-containing particle, and a syrup, and dry ingredients. Inthe preparation of the bar the pretreated antioxidant and the syrup arecombined to form a binder which is added to the dry ingredients. Theoptional ingredients for inclusion in the pretreated antioxidant orantioxidant particles, the syrup, and the dry ingredients are shown.

A further advantage of the pretreatment process, in addition toconservation of cocoa procyanidins, is that it permits the preparationof two heated liquid streams which in the preferred embodiment formaking granola bars are blended at the last possible moment. Both thepretreated cocoa solids and the syrup streams are much lower inviscosity than their combination. This facilitates using conventionaltanks, lines, and positive-displacement pumps, as well as keeping thepressure drop in the piping within reasonable limits. The two heatedliquid streams can be blended in-line, provided they are delivered inthe desired proportions. Suitable equipment for in-line mixing isreadily available, and due to its compact size, can be located inproximity to the point of use where the binder syrup (i.e., combinedstreams) is combined with the dry ingredients (grains, dried fruits andnuts and the like) to make confectionery products.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the term “antioxidant” refers to compounds that preventoxidation and function as a reducing agent or as an electrondonor/receptor. According to their mode of action, antioxidants may beclassified as free radical terminators, metal ion chelators, or asscavengers that react with oxygen. Suitable antioxidants classes includetannins, including condensed tannins and hydrolyzable tannins, quinones,polyhydroxy compounds, phospholipids, tocol compounds or derivativesthereof. Exemplary antioxidants include, but are not limited to,butylated hydroxyanisole, butylated hydroxytoluene, tertiary butylatedhydroquinone, propyl gallate, a phenolic acid, a polyphenol, ascorbicacid, stannous chloride, a tocopherol, sulfur dioxide, and dilaurylthiodipropionate. The antioxidants and antioxidant-containing particleshave particle sizes of up to about 150 microns, typically about 5 toabout 70 microns.

As used herein, “food” is a material consisting of protein, carbohydrateand/or fat, which is used in the body of any organism to sustain growth,repair vital processes, and to furnish energy. Foods may also containsupplementary substances, such as minerals, vitamins, and condiments(Merriam-Webster Collegiate Dictionary, 10^(th) Edition, 1993).

As used herein, “food supplement” is a product (other than tobacco) thatis intended to supplement the diet that bears or contains one or more ofthe following dietary ingredients; a vitamin, a mineral, an herb orother botanical, an amino acid, a dietary substance for use by man tosupplement the diet by increasing the total daily intake, or aconcentrate, metabolite, constituent, extract or combination of theseingredients. (Merriam-Webster Collegiate Dictionary, 10^(th) Edition,1993). When the term is used on food labels, “supplement” means thatnutrients have been added in amounts greater than 50% above the U.S.Recommended Daily Allowance (“Understanding Normal and ClinicalNutrition”, 3^(rd) Edition, Editors Whitney, Catalado and Rolfes at page525).

The present invention relates to products such as foods or foodsupplements, other than beverages or beverage mixes, which containantioxidants, preferably cocoa polyphenols, in combination with selectedsterol ester(s) and/or stanol ester(s). The products may optionallycontain L-arginine, minerals such as calcium, potassium and magnesium,vitamins such as B, C, and E, a carotenoid, and mono- or polyunsaturatedfatty acids (e.g., an omega-3 fatty acid). Products containingpolyphenols from sources other than cocoa which have antioxidantproperties similar to those of cocoa polyphenols (for example, nuts, nutflours, and nut skins) may also be used in combination with the cocoapolyphenols. Cholesterol-lowering agents other than sterol/stanol estersmay be used herein in combination with the sterol ester(s) and/or stanolester(s). Examples include low caloric and non-caloric fats.

As used herein, the term “cocoa polyphenols” refers to polyphenoliccompounds including proanthocyanidins, more particularly procyanidins,present in cocoa beans, cocoa nibs, cocoa ingredients prepared fromcocoa beans or nibs, and cocoa extracts prepared from cocoa beans orcocoa ingredients. The term “procyanidin” refers to naturally occurringor synthetically derived oligomers of catechin and/or epicatechin;however, any reference to “cocoa procyanidins” herein should beunderstood to also include the monomers catechin and epicatechin. Themonomers include (+)-catechin, (−)-epicatechin and their respectiveepimers (e.g. (−)-catechin and (+)-epicatechin). The monomers have thestructure:

Procyanidin oligomers may have from 2 to about 18 monomeric units. Theoligomers include, for example, dimers, trimers, tetramers, pentamers,hexamers, heptamers, octamers, nonamers, decamers, etc. In the naturaloligomer, the monomers are connected via (4→6) and/or (4→8) interflavanlinkages. Oligomers with exclusively (4→8) linkages are linear. Thepresence of at least one (4→6) linkage results in a branched oligomer.For the synthesis of 4→8 procyanidins, see U.S. Pat. No. 6,420,572issued Jul. 16, 2002 to L. J. Romanczyk, Jr. et al., the disclosure ofwhich is incorporated herein by reference, The '572 patent disclosescoupling hydroxy-protected phenolic monomers (e.g., epicatechin orcatechin) having a C-4 activating group (e.g., a C₂-C₆ alkoxy grouphaving a termimal hydroxy group such as hydroxyethoxy) with a secondprotected phenolic monomer to prepare protected dimers which are thendeprotected or optionally coupled with other protected, activatedphenolic monomers.

Cocoa polyphenol derivatives may also be useful. These include gallatedcatechin and/or epicatechin monomers and oligomers, glycosylatedmonomers and oligomers, and mixtures thereof; metabolites of theprocyanidin monomers and oligomers such as sulfated, glucoronidated, andmethylated forms; and enzyme cleavage products of procyanidins generatedby colonic microflora metabolism or internal mammalian metabolism. Thederivatives may be from natural sources or prepared synthetically.

Synthetic oligomers are also useful herein. See U.S. Pat. No. 6,156,912issued Dec. 5, 2000 to W. Tückmantel et al. and U.S. Pat. No. 6,476,241issued Nov. 5, 2002 to A. Kozikowski et al.

The term “fair average quality cocoa beans” refers to cocoa beans thathave been separated from the pulp material and dried and are relativelyfree of mold and infestation. Such beans are a commercial commodity andform the feedstock for preparing high CP cocoa solids. The term includesany such bean that has been genetically modified or produced.

The term “raw freshly harvested cocoa beans” refers to seeds or beansfreshly harvested from the cocoa pod and which have not been subjectedto processing other than separation from the pulp. The term includes anysuch bean that has been genetically modified or produced.

As used herein, the term “cocoa solids” refers to partially or fullydefatted cocoa solids (e.g., cake or powder) prepared directly by screwpressing shelled cocoa beans into cocoa butter and partially defattedcocoa solids or by milling roasted cocoa beans into chocolate liquor andpressing the chocolate liquor to recover cocoa butter and partiallydefatted cocoa solids.

As used herein, the term “high CP cocoa solids” refers to cocoa solidsin which the cocoa procyanidin content is conserved during thepreparation of the cocoa solids and/or to cocoa solids prepared fromunfermented, underfermented, or fair to average quality (FAQ) cocoabeans.

Cocoa beans from any species of Theobroma, Herrania or inter- andintra-species crosses thereof may be used to prepare cocoa solids andchocolate liquor for use herein. Preferably, the cocoa solids areprepared from unfermented and/or underfermented cocoa beans, i.e., slatycocoa beans, purple cocoa beans, mixtures of slaty and purple cocoabeans, mixtures of purple and brown cocoa beans, or mixtures of slaty,purple, and brown cocoa beans. More preferably, the cocoa beans areslaty and/or purple cocoa beans have a higher cocoa polyphenol contentthan fermented beans. The chocolate liquor is preferably prepared fromroasted, fermented cocoa beans because the flavor/aroma of the roasted,fermented cocoa beans is better.

The cocoa polyphenol content of cocoa ingredients is higher when thecocoa beans or blends thereof have a fermentation factor of 275 or less.Preferably, these cocoa beans are used for processing into high CP cocoasolids. The “fermentation factor” is determined using anindustry-recognized grading system. To assess the degree offermentation, cocoa beans are typically subjected to a standard cut testfor assessing quality as defined by standards.

A method for preparing cocoa solids having a high cocoa polyphenolcontent directly from cocoa beans is disclosed in U.S. Pat. No.6,015,913 issued Jan. 18, 2000 to Kirk S. Kealey et al., the disclosureof which is incorporated herein by reference. In the process of the '913patent, the cocoa beans are heated for a time and at an internal beantemperature sufficient to loosen cocoa shell without roasting the cocoanib (e.g., infra-red heating to about 100° C. to about 110° C.). Thecocoa nibs are winnowed from the cocoa shells. The cocoa nibs are screwpressed into the cocoa butter and the partially defatted cocoa solids.The cocoa solids contain cocoa polyphenols including cocoa procyanidinsfrom the cocoa nibs. Much higher levels of the higher procyanidinoligomers are present in the cocoa solids thus produced then are presentin cocoa solids prepared by a traditional roasting process. The totalcocoa procyanidin amounts in the cocoa solids are determined asdescribed hereafter. The method for determining the internal beantemperature (IBT) is described in the '913 patent.

A method for preparing cocoa solids or chocolate liquor from roastedunfermented, underfermented, or fair to average quality cocoa beans isdisclosed in U.S. Pat. No. 6,312,753 issued Nov. 6, 2001 to Kirk S.Kealey et al., the disclosure of which is incorporated herein byreference. Cocoa beans or nibs having a fermentation factor of 275 orless. The beans are passed through an infra-red heater, and winnowed toseparate the shell (hull), roasted to an internal bean temperature ofabout 95° C. to about 150° C., and milled into a course chocolate liquorfrom which the cocoa butter and partially defatted cocoa solids arepressed.

The chocolate liquor may also be prepared from cocoa beans that havebeen processed using traditional cocoa processing methods (described,for example, in Industrial Chocolate Manufacture and Use, ed. Beckett,S. T., Blackie Acad. & Professional, New York, 1997, such as in Chapters1, 5 and 6) or using the improved processing method described in the'913 patent discussed above.

If desired, a cocoa extract can be included in the products herein. Thepreparation of cocoa extracts from cocoa beans is disclosed in U.S. Pat.No. 5,554,645 issued Sep. 10, 1996 to Leo J. Romanczyk, Jr. et al., thedisclosure of which is incorporated herein by reference. In the processof the '645 patent cocoa beans including the pulp are freeze dried, thefreeze dried mass is depulped, the freeze dried cocoa beans are dehulledand ground, and the resulting cocoa mass is defatted and then solventextracted, for example with aqueous methanol, aqueous acetone, or ethylacetate. Extracts can also be prepared from high CP cocoa solidsprepared by the processes described in the '913 and '753 patentspreviously discussed. Improved processes for preparing cocoa extractsenriched in certain oligomers, as well as decaffeinated anddetheobrominated cocoa extracts, are described in U.S. Ser. No.09/590,931 filed Jun. 9, 2000, now allowed, the disclosure of which isincorporated herein by reference.

Pretreated Cocoa Antioxidant Mixture

This mixture, also referred to as the fat phase, contains no addedmoisture.

Fats and/or Oils

Antioxidants or antioxidant-containing particles, such as high CP cocoasolids are pretreated with a food-grade fat or oil to protect theparticles during further processing into a food, a food supplement, or afood additive. Pretreatment by mixing with the fat or oil prevents theloss of cocoa procyanidins. The antioxidants or antioxidant-containingparticles are mixed with about 9 to about 90%, typically about 15-80%,preferably about 25-70%, more preferably about 40-60% of the fat and/oroil. If not liquid at room temperature, the fats should be liquifiableat about 70°-80° C., preferably at about 60° C.

Preferred antioxidants, including the preferred cocoa solids, arediscussed above. Preferred fats and oils include sterol ester(s) and/orstanol ester(s) and vegetable oils such as corn, soya, cocoa butter andcocoa oil, coconut oil, and palm kernel oil. The most preferred aresterol ester(s) and/or stanol esters which are added as acholesterol-lowering agent as well as as a pretreatment ingredient forprotecting the antioxidant and high CP cocoa solids.

Phytosterols are plant sterols that do not dissolve in water and have amolecular weight and structure similar to cholesterol. Over forty plantsterols have been identified but beta-sitosterol, campesterol andstigmasterol are the most abundant. Other examples of useful sterols arebrassicasterol, desmosterol, chalinosterol, poriferasterol, andclionasterol.

Stanols are saturated derivatives of sterols in which all carbon-carbonbonds in the rings are saturated. Stanols typically have 28 or 29 carbonatoms and include beta-sitostanol, clionastanol,22,23-dyhydrobrassicastanol and campestenol. Stanols are found in smallamounts in nature but may be easily prepared from sterols byhydrogenating sterols by any of the several methods known to thoseskilled in the art. When a sterol starting material is prepared from aplant material it will contain a mixture of several different sterolsthus, after hydrogenation, the resulting stanol will also be a mixtureof different stanols.

Cocoa oil extracted from cocoa hulls is also a good source ofphytosterols. Cocoa phytosterols are a mixture of free and boundsterols, with the free sterols being up to about 90% of the phytosterolspresent. The phytosterols include campesterol, β-sitosterol,stigmasterol, cycloartenoyl, 24-methylene cycloartenoyl, as well asminor amounts of other phytosterols. The bound phytosterols include thefatty acid esters or ferulate derivatives of the phytosterols.

Esterified forms of sterols and stanols are the forms used herein.Esterification renders the sterols/stanols more soluble in fats andoils. For example, sterols may be esterified with fatty acid esters suchas rapeseed oil, canola oil, and like oils. Suitable fatty acids includesaturated or unsaturated fatty acids typically having 14 to 24 carbonatoms. Examples of esterified sterols include sitosterol acetate,sitosterol oleate and stigmasterol oleate. Stanol esters may be preparedas is known in the art and, as for example, described in U.S. Pat. No.6,174,560 issued Jan. 16, 2001 to Miettenen et al. and assign ed toRaisio Benecol Ltd.; U.S. Pat. No. 6,031,118 issued Feb. 29, 2000 to vanAmerongen et al. and assigned to Lipton; U.S. Pat. No. 5,958,913 issuedSep. 28, 1999 to Miettenen et al. and assigned to Raisio Benecol; U.S.Pat. No. 5,892,068 issued Apr. 6, 1999 to Higgins, III and assigned toMcNeil PPC, Inc.; and U.S. Pat. No. 5,502,045 issued Mar. 26, 1996 toMiettenen et al. and assigned to Raisio Benecol, Ltd., the disclosuresof which are incorporated herein by reference. The '045 patent describesthe interesterification of free stanols with a methyl ester mixture ofC₂ to C₂₂ fatty acids (e.g., rapeseed oil) using an interesterificationcatalyst such as sodium ethylate. An interesterification process such asthat disclosed in the '045 patent can also be used to esterify sterolesters. In another embodiment, useful stanol esters are prepared byesterifying at least one sterol with a C₂ to C₂₂ fatty acid ester asdescribed in the '913 patent cited above.

Particularly useful herein are canola oil sterol esters, sunflower oilsterol esters, and their mixtures. These sterol ester mixtures melt ataround 30°-50° C.; however, typically the esters are heated to about60°-80° C. to ensure the entire mixture is liquified. The liquid orliquefied sterols/stanol esters are mixed with the high CP cocoa solidsto protect the CPs during the further processing of the cocoa solidsinto the final products prevents this loss about. When not pretreated,up to about 40% to about 90% of the cocoa procyanidins can be lostduring processing of the cocoa solids into the final product, dependingon processing conditions such as temperature and shear. It is believedthat the CPs are moisture-sensitive and that pretreatment with steroland/or stanol esters prior to contact with the aqueous syrup used in thepreparation of the products protects the CPs. When the processesdescribed herein are followed, at least 65% of the cocoa procyanidinsare conserved. Typically, about 80% to about 90% of the cocoaprocyanidins are conserved. More preferably, about 90% to 100% arepreserved.

Emulsifier(s)

Preferably, an emulsifier such as lecithin, a mono- or diglyceride,mono- or diglyceride, a phospholipid, an ester of a monoglyceride andacetic, lactic, citric, succinic, or tartaric acid, a fatty acid esterof a polyglycerol, sorbitol esters, sucrose esters, propylene glycol, orpolyglycerol polyresorcinoleate is also premixed with the sterol and/orstanol esters and chocolate liquor before addition to the cocoa solids.The emulsifier is used in amounts of about 0.05% to about 5%, preferablyabout 0.05% to about 1%, more preferably about 0.05% to about 0.25%.Emulsifying agents are well known to play a critical role in suspensionrheology and are used throughout food manufacturing, especiallyconfectionery and chocolate manufacturing, to enhance the rheology(i.e., reduce viscosity and/or yield value) of solids suspensions.

Lecithin derived from vegetable oils, e.g., soybean, cottonseed, corn,safflower, and rapeseed oil, including clarified lecithins, fluidizedlecithins, compounded lecithins, hydroxylated lecithins, deoiledlecithins, and fractionated lecithins are useful herein. Soy lecithin isthe preferred emulsifier for use herein. It is one of the oldest andmost widely used emulsifying agents. In chocolate, lecithin demonstratesa significant viscosity lowering effect. It can be used in amounts of upto about 5%, preferably about 0.05% to about 0.3%, more preferably about0.1% to about 0.3% by weight, based on the finished chocolate.

When a reduced fat food is prepared, a combination of emulsifying agentsis used, i.e., a base emulsifying agent and a second emulsifying agent.The base emulsifying agent is added in an amount of less than 1.0% byweight. The amount of the base emulsifying agent present in thereduced-fat chocolates is about 0.1% to about 0.9%, preferably about0.2% to about 0.8%, and more preferably about 0.4% to about 0.6% byweight, based on the total weight of the chocolate. Selectedcombinations of emulsifying agents have been identified for use inreduced-fat confectioneries, having improved rheology. Emulsifying agentcombinations that are particularly useful are combinations of lecithin,sucrose polyerucate, sucrose polystearate, ammonium phosphatide,phosphated mono-di-glycerides/diacetyl tartaric acid of monoglycerides,or fractionated lecithin, with sucrose polyerucate and/or polyglycerolpolyricinoleate. The rheology of reduced-fat chocolates may be furtherimproved using a three component emulsifier combination. The preferredcombinations include lecithin-sucrose polyerucate, lecithin-polyglycerolpolyricinoleate, sucrose polyerucate-polyglycerol polyricinoleate, andlecithin-sucrose polyerucate-polyglycerol polyricinoleate.

Chocolate Liquor

Preferably chocolate liquors such as those discussed above are includedwith the pretreated cocoa solids in amounts of up to 20%, typicallyabout 0.5% to about 10%, and more preferably about 0.5% to about 3%. Ofcourse, the amount of cocoa solids and chocolate liquor used will dependupon the type of product being prepared.

Syrup

The syrup comprises an aqueous solution of nutritive carbohydratesweetener(s) and/or sugar substitute(s).

Nutritive carbohydrate sweeteners, with varying degrees of sweetnessintensity are useful herein. Preferably, the sweetener comprises a cornsyrup or a blend of corn syrups and another sweetener. Suitablesweeteners include those typically used in foods and include, but arenot limited to, sucrose (e.g., from cane or beet), dextrose, fructose,lactose, maltose, glucose syrup or the solids thereof, corn syrup or thesolids thereof, invert sugar, hydrolyzed lactose, honey, maple sugar,brown sugar, molasses and the like.

Sugar substitutes may be used to partially replace the sweetener in thesyrup, particularly in the production of reduced-calorie products. Theterm “sugar substitute” includes high potency sweeteners, sugar alcohols(polyols) and bulking agents, or combinations thereof. The high potencysweeteners include aspartame, cyclamates, saccharin, acesulfame,neo-hesperidin dihydrochalcone, sucralose, alitame, stevia sweeteners,glycyrrhizin, thaumatin, and the like, and mixtures thereof. Thepreferred high potency sweeteners include aspartame, cyclamates,saccharin, and acesulfame-K. Examples of sugar alcohols may be any ofthose typically used in the art and include sorbitol, mannitol, xylitol,maltitol, isomalt, lactitol and the like. The food products of thepresent invention may also contain bulking agents, typically used incombination with high potency sweeteners. The term “bulking agents” asdefined herein may be any of those typically used in the art and includepolydextrose, cellulose and its derivatives, maltodextrin, gum arabic,and the like.

Typically, the syrup comprise about 5% to 100% of corn syrup solids andup to 80% sugar, based on the total weight of the syrup. For the foodbars, the corn syrup is about 5% to 100%, preferably about 65% to about98%, and most preferably about 80% to about 95% and the sugar is up toabout 20%, preferably about 1% to about 10%, and more preferably about1% to about 5%. For a chocolate confectionery such as a chew, the cornsyrup is about 5% to about 80%, preferably about 10% to about 50%, andmost preferably about 20% to about 35%.

Minor amounts of other water-soluble or water-dispersible ingredient arealso included in the syrup, for example up to 15% of vitamins and/orminerals, up to 1% of a flavorant, and up to 3% of a salt.

As used herein, the term “flavoring agent” refers to flavored compoundsor compositions used in food or food supplement to impart a desiredtaste and/or aroma. Exemplary flavoring agents suitable for use hereininclude vanillin, raspberry spices, and naturally expressed citrus orspice oils.

Binder Syrup

The binder syrup comprises the syrup and the pretreated solids (e.g., aparticulate antioxidant or antioxidant-containing particles such ascocoa solids is formulated to first coat the dry ingredient and then“set” or harden to hold the final product in the desired shape. Thebinder syrup can also carry other water-soluble or water-dispersibleingredients such as flavorants. Typically, a sugar-based syrup thathardens when cooled is used. In ready-to-eat snack foods. The bindersyrups contain about 50% to about 85%, preferably about 60% to about80%, more preferably about 65% to about 80%, and most preferably about70% to about 75% by weight of the syrup and about 15% to about 50%,preferably about 20% to about 40%, more preferably about 25% to about40%, and most preferably about 25% to about 30% by weight of pretreatedsolids. The percentages are by weight and total 100%. The moisturecontent of the binder syrup is about 1% to about 15%, preferably about3% to about 12%, and most preferably about 5 to about 10%.

Dry Ingredients

Any suitable grain, flour, and/or protein can be used in theready-to-eat food bars. Typical grains include flaked oats, wheat,barley, and rye, toasted rolled oats, crisped rice and the like. Typicalflours include bran, corn, wheat, and rice. Typical proteins includesoy, whey, milk, peanut, and egg proteins. Optional dry ingredientsinclude chopped or whole nuts, such as almonds, hazelnuts, peanuts, andcoconut flakes, dried fruits such as blueberries and cherries, andchocolate chips. The binder syrup comprises about 30% to about 75%preferably about 40% to about 65%, more preferably about 50% to about60%, and most preferably 55% by weight of the bar. Preferably, thegranola bar with or without fruit and/or nut inclusions is enrobed ordecorated with chocolate, preferably a tempered dark chocolate, yogurt,or flavored granulated sugars.

If desired, the granola bar can contain supplemental dietary fiber(s)which are added in the form of compressed flakes. As used herein, theterm “supplemental dietary fiber” refers to dietary fibers which areadded to the bar apart from the fiber which is typically included in agranola bar. The supplementary dietary fibers can be of various typesand preferably are a mixture of various types and, more preferably, amixture of soluble and insoluble dietary fibers. Sources generally knownto contribute insoluble fiber include, but are not limited to, soyfiber, apple fiber, corn bran, wheat bran, oat bran, barley bran, ryebran, triticale bran, cellulose, pea fiber, sugar beet fiber, and peanutfiber. Sources generally known to contribute soluble fiber include, butare not limited to, gum arabic, gum ghatti, guar gum, pectins, psyllium,carrageenans, xathan, tragocanth, karaya, locust bean gum, agar, andalginates.

Ready-To-Eat Products

The food products prepared herein have a reduced water availability toprevent microbial growth and lengthen shelf life. Such availability ofwater in a food is commonly termed “water activity” (A). In general, alow A food product (under 0.90) indicates the existence of anenvironment in which most bacteria will not generally grow, and 0.1-0.55is preferred.

The term “chocolate” is intended to refer to all chocolate orchocolate-like compositions with a temperable fat phase. As theinvention is directed to the control of the characteristics of the fator fat-like phase of the chocolate, rather than the non-fat materialswithin the chocolate, the term is intended to include all chocolate andchocolate-like compositions that contain at least one cocoa orcocoa-like component in the temperable fat or temperable fat-like phase.The term is intended, for example, to include standardized andnon-standardized chocolates, i.e., including chocolates withcompositions conforming to the U.S. Standards Of Identity (SOI) andcompositions not conforming to the U.S. Standards Of Identity,respectively, including dark chocolate, baking chocolate, milkchocolate, sweet chocolate, semi-sweet chocolate, buttermilk chocolate,skim-milk chocolate, mixed dairy product chocolate, low fat chocolate,white chocolate, non-standardized chocolates and chocolate-likecompositions, unless specifically identified otherwise.

Reduced fat chocolates comprise a fat, solid containing chocolateingredients, and a combination of a base emulsifying agent and at leastone other emulsifying agent. The chocolates are prepared by mixing thefat and chocolate ingredients, adding the base emulsifying agent to themixture; and then adding at least one other emulsifying agent. Theresulting confectioneries have the texture of a full-fat confectionery.

Chocolate may take the form of solid pieces of chocolate, such as barsor novelty shapes, and may also be incorporated as an ingredient ofother, more complex confections where chocolate is combined with andgenerally coats other foods such as caramel, peanut butter, nougat,fruit pieces, nuts, wafers, ice cream or the like. These foods arecharacterized as microbiologically shelf-stable at about 65° to about85° F. (18° to 29° C.), under normal atmospheric conditions.

The syrup is about 50% to about 85%, preferably about 60% to about 80%,more preferably about 65% to about 80%, and most preferably about 70% toabout 75% of the chew. The cocoa solids are about 15% to about 50%,preferably about 20% to about 40%, more preferably about 25% to about30% of the chews. The percentages are by weight and total 100%. Themoisture content of the syrup is about 1% to about 15%, preferably about3% to abut 12%, and most preferably about 5% to about 10%.

When chocolate chews are prepared, the pretreated cocoa solids and thesyrup are combined at a temperature of about 20° C. to about 160° C.,preferably about 50° C. to about 120° C., more preferably about 80° C.to about 110° C. and then cooled to about 5° C. to about 60° C.,preferably about 15° C. to about 40° C., and more preferably about 20°C. to about 30° C. and then shaped.

When granola bars are prepared, preferably the pretreated cocoa solidsand syrup are combined immediately before addition to the solidsingredients and the resulting binder syrup is then added to the dryingredients. The combining and cooling temperatures discussed above aresuitable for the bars.

Test Methods Determination of Cocoa Procyanidin Content

The cocoa procyanidin content of the cocoa solids, binder syrup,chocolate foods (e.g., granola bars), and chocolate confectioneries(e.g., dark or milk chocolate chews) was determined by normal phase highpressure liquid chromatography (HPLC) on silica with fluorescentdetection. The details of this approach are covered in Adamson, G. E.,Lazarus, S. A., Mitchell, A. E., Prior, R. L., Cao, G., Jacobs, P. H.,Kremers B. G., Hammerstone, J. F., Rucker R., Ritter. K. A., Schmitz, H.H., HPLC Method for the Quantification of Procyanidins in Cocoa andChocolate Samples and Correlation to Total Antioxidant Capacity, J. Ag.Food Chem.; 1999; 47 (10) 4184-4188. Cocoa solids were defatted withhexane prior to extraction of the procyanidins. Binder syrup and thechocolate products (e.g., chocolate chews and chocolate granola bars)were cyro-ground to a fine powder and immediately extracted with 70%acetone, 29.5% water, and 0.5% acetic acid. The binder syrup andfinished products were not defatted prior to procyanidin extraction.Cocoa procyanidin quantitation was achieved through the use of a wellcharacterized composite reference standard material. Samples were thencompared with the composite standard to accurately determine the levelsof procyanidins.

Determination of Methylxanthines in Cocoa Solids

The theobromine and caffeine content of cocoa solids prepared fromvarious cocoa beans was determined using the procedure described below.The solids are typically defatted first by extraction with hexane.

The theobromine and caffeine contents were analyzed according to §35LMBG “Amtliche Sammlung von Untersuchungsverfahren” L-18.00-16Bestimmung von Theobromin und Coffein in feinen Backwaren” Cocoa Atlas2002, Methodology—p. 17, 2002 Foundation of the German Cocoa andChocolate Industry and Prof. Dr. R. Lieberei, Dipl.-Biol. C. Rohsius.The determination of theobromine and caffeine was carried out by meansof the RP-HPLC with UV-detection.

A total of 0.500 g defatted, milled cocoa powder was mixed with 160 ml.boiling distilled water in a 200 ml graduated flask and put in a boilingwater bath for 30 min. being occasionally stirred. Subsequently, thesample was cooled down to 20° C. purified by 1 ml Carrez 1(K₄[Fe(CN)₆]×3 H2O; β=150 g/l) and 1 ml Carrez II (ZnSO₄×7 H₂O; β=300g/l), filled with distilled water and shaken. Then, it was filteredthrough a soft folded filter (Schleicher & Shuell 595½) and 3 ml of thefiltrate were diluted with distilled water to attain a total quantity of25 ml. For the HPLC analysis, it was filtered by a 0.045 μm filter.

HPLC - conditions Separating column: Lichrospher 60 Rp select; B 5 μm;250 mm × 4 mm Elution solution: CH₃CN/methanol/0.02 M phosphate-bufferpH 4: 7 + 3 + 90 (v/v/v) Velocity of flow: 0.8-1.4 ml/min Injectionvolumn: 20 μl Temperature: Column temperature: 30° C./35° C. isocraticmeasurement Detection: 274 nm Pump: Knauer HPLC pump 64.20 μl-chargingvalve (loop) Autosampler: Waters Model 717 Plus Solution degaser:Degassex DG-4400, Phenomenex Set-up Calibration: See 4.5 § 35 LMBG -regulation Set-up PO₄-buffer See 4.9 § 35 LMBG - regulation (subsequentsolution: filtration by a 0.45 μm filter) Quantification Peak area

LOCATION THEOBROMINE CAFFEINE Central America Dominican Republic  1.2%0.17% Ecuador 1.44% 0.29% Haiti Venezuela West Africa Ivory Coast 1.19%0.13% Ghana 1.31% 0.10% Cameroon 1.46% 0.06% Nigeria 1.49% 0.12% Togo1.28% 0.08% Sierra Leone 1.27% 0.07% Southwest Asia Indonesia 1.31%0.14% Malaysia 1.13% 0.14% Apua New Guinea* 0.80% 0.15% Solomon Islands*0.90% 0.06% *Sour over-fermented cocoa beans (FF of 375-400)

While the theobromine and caffeine content of cocoa beans vary with thebeans origin and fermentation factor, the content does not changemarkedly during the processing of cocoa solids or chocolate liquor intoa final food product. Thus, unlike cocoa procyanidins the percentage ofthe methylxantines in a final cocoa product can be used to determine theamount of cocoa solids or chocolate liquor used to prepare the finalchocolate product. Typically, the theobromine ranges from 1.13% to 1.49%and the caffeine from 0.06 to 0.29%.

The examples which follow are intended as an illustration of certainpreferred embodiments of the invention, and no limitation of theinvention is implied.

EXAMPLE 1 Method for Preparing High CP Cocoa Solids from Cocoa Beans

Commercially available cocoa beans having an initial moisture content ofabout 7 to 8% by weight are pre-cleaned in a scalperator. Thepre-cleaned bean from the scalperator are further cleaned in an airfluidized bed density separator. The cleaned cocoa beans are then passedthrough an infra-red heating apparatus at a rate of about 1,701kilograms per hour. The depth of beans in the vibrating bed of theapparatus is about 2-3 beans deep. The surface temperature of theapparatus is set at about 165° C., thereby producing an internal beantemperature (IBT) of about 135° C. in a time ranging from 1 to 1.5minutes. This treatment causes the shells to dry rapidly and separatefrom the cocoa nibs. The broken pieces separated by the vibrating screenprior to the apparatus are re-introduced into the product stream priorto the winnowing step. The resulting beans after micronizing should havea moisture content of about 3.9% by weight. The beans emerge at an IBTof about 135° C. and are immediately cooled to a temperature of about90° C. in about three minutes to minimize additional moisture loss. Thebeans are then winnowed to crack the beans to loosen the shells andseparate the lighter shells from the nibs while at the same timeminimizing the amount of nib lost with the shell reject stream.

The resulting cocoa nibs are pressed using two screw presses to extractthe butter from the cocoa solids.

A sample of cocoa solids, produced according to the above-describedprocess from unfermented cocoa beans (fermentation factor 233), whenanalyzed according to the above-referenced method, typically will have atotal cocoa procyanidin content of about 50 to about 75, preferablyabout 60 to about 75, or more preferably about 75 to about 80 milligramstotal cocoa procyanidins per gram of defatted cocoa powder.

EXAMPLE 2 Production of Chocolate Liquor Containing Cocoa Polyphenols

Fair average quality (FAQ) cocoa beans having an initial moisturecontent of 7.4% by weight and a fermentation factor level of 233 (31%slaty, 29% purple, 22% purple brown, and 17% brown) are selected as thestarting material. The cocoa beans are then passed through an infra-redheating apparatus. The feed rate of beans through the infra-red heaterand the infra-red heater bed angle are varied to control the amount ofheat treatment the beans receive. The amount of time the beans spend inthe infra-red heater (residence time) is determined by the bed angle andthe feed rate. The times that should be used to prepare the samplematerial are listed in the table below. At the outlet of the micronizerthe IBT of the beans is measured. Expected values are also shown in thetable.

A 1 kg sample of infra-red heated beans, collected off the infra-redheater at different IBTs, are cracked into smaller pieces to facilitatethe separation of the nib from the shell. The cracked beans are thenpassed through a laboratory scale winnowing system. The cocoa nibs arethen crushed and milled into a coarse chocolate liquor. The normaloperating temperature for the liquor in the crusher is approximately 50°C. The cocoa nibs are ground for one hour. The expected cocoa polyphenolvalues are shown below.

% Moisture mg/g of Total Cocoa TABLE Residence Time in in FinishedProcyanidins in Defatted IBT° C. Micronizer, Seconds Liquor Cocoa Powder107 42 3.9 67.3 126 82 1.87 48.9 148 156 1.15 40.7

EXAMPLE 3 Chews Containing Sterol Esters in Combination with High CPCocoa Solids

The chews were prepared from the ingredients shown below by pre-mixingsterol esters, cocoa solids, lecithin, and dark chocolate liquor or milkchocolate liquor, for example in Z-blade mixer, to prepare thepretreated cocoa solids. The pretreated cocoa solids were incorporatedinto a cooked syrup (heated to 66° C.) containing the remainingingredients. The moisture content of the syrup was about 9%. The mixturewas slowly cooled, rolled, and wrapped. The moisture content of thefinal mixture was about 8.3-8.7%.

The cocoa solids used to prepare the chews had a cocoa procyanidincontent of about 50 to about 80 milligrams per gram of defatted cocoasolids. The canola sterol esters used to prepare the chews were suppliedby Raisio Benecol Ltd., Finland or Raisio Staaco U.S., Inc. They had amelting point of about 30° C. and were heated at about 50-60° C. toensure complete liquification. The phytosterols present in the mixtureinclude B-sitosterol (50.6%), campestoerol (27.6%), stigmasterol(16.8%), and other sterols (5%) esterified using the interesterificationprocess described in U.S. Pat. No. 5,502,045 issued Mar. 26, 1996.

Dark Chocolate Chew

% Formula Corn Syrup (63 D.E.) 27 Sugar (Cane or Beet) 21 SweetenedCondensed Skim Milk 15 Dark Liquor 20 Cocoa Powder (10-12% fat) 8 CanolaSterol Esters 6 Solid Vitamin Premix 2 Vanilla Ice Cream Flavors 0.75Soy Lecithin 0.125 Salt-Flour 0.125

Milk Chocolate Chew

% Formula Corn Syrup (63 D.E.) 27 Sugar-Cane or Beet 21 SweetenedCondensed Skim Milk 15 Milk Chocolate Liquor 12 Water 8 High CP CocoaPowder (10-12% fat) 8 Canola Sterol Esters 6 Solid Vitamin Premix 2Vanilla Ice Cream Flavors 0.75 Soy Lecithin 0.125 Salt-Flour 0.125

EXAMPLE 4 Chocolate Granola Bars

A syrup containing all the minor ingredients (i.e., vitamin mixture,brown sugar, salt vanilla) dissolved or dispersed in the corn syrups wasprepared by blending the ingredients at about 55° C. for 15 minutes in ahigh speed mixer. The high CP cocoa solids were mixed with a mixture ofthe canola sterol esters, chocolate liquor, and lecithin and blendedbriefly, e.g., for about 15 minutes in a high speed mixer to create thepretreated cocoa solids. The aqueous syrup stream and pretreated cocoasolids streams were mixed at the last possible moment, in an in-linemixer to create binder syrup and then blended with the dry ingredients(i.e., rice, soy, oats, and optional almonds, cherries, andblueberries). The blend was deposited as a slab, compressed, slit intobars, and cooled.

Granola Bars

Formula (%) Pretreated Cocoa Solids High CP Cocoa Powder* 8 CanolaSterol Esters* 7 Chocolate Liquor 1.5 Soy Lecithin 0.2 Syrup Corn Syrup(55 DE) 17 Corn Syrup (63 DE) 9 Vitamin Premix 2.4 Fructose 1.1 Salt 0.4Brown Sugar 0.3 Vanilla Ice Cream Flavors 0.1 Water 9 Dry IngredientsSoy Crisp 11 Crisp Rice 9 Oats 6 Enrobing Ingredient Chocolate 18 *Seedescription in Example 3

Chocolate almond crunch bars were prepared by adding 5-20%, preferablyabout 7-14%, chopped almonds to the dry mix. Similarly chocolateblueberry crunch bars and chocolate cherry crunch bars were prepared byadding 4-20%, preferably 6-14% of dried blueberries or cherries to thedry mix.

EXAMPLE 5 Preparation of Binder Syrups

Two binder syrups of identical composition were prepared to compare theeffect of pretreating high CP cocoa solids. The formulation is the sameas that used in Example 4 except the dry ingredients (soy crisp, crisprice, and oats) were not used. In the comparative binder syrup, thesyrup ingredients as well as the high CP cocoa solids, sterol esters,chocolate liquor, and soy lecithin were all mixed in one step. In theinventive binder, the pretreated high CP cocoa solids were preparedseparately, the syrup was prepared separately, and then the two liquidswere combined. In both tests all materials were maintained at atemperature between 50 and 60° C.

The average cocoa procyanidin content of binder syrups containingpretreated and untreated cocoa solids was determined using theanalytical procedure described above. The results are set out below.

Total Cocoa Procyanidins (mg./g of Binder Syrup)

Syrup Syrup Prepared Prepared with Mixing with % Retained PretreatedRetained (minutes) Untreated Cocoa Cocoa Cocoa Time Cocoa SolidsProcyanidins Solids Procyanidins 0 10 — 10 — 15 9.04 90% 10.07 100%retained 60 6.78 68% 9.87 99% 120 5.91 59% 9.12 90% 180 5.75 58% 8.8789% 240 5.75 58% 8.86 89%

The results show that when untreated cocoa solids were used, about 10%of the cocoa procyanidins were lost during the first 15 minutes ofmixing and that about 32% were lost after only 60 minutes of mixing. Thegreatest loss (42%) occurred after 3 hours of mixing. The syrup preparedfrom the pretreated cocoa solids showed no loss until 60 minutes. Fromat least 89% to 100% of the cocoa procyanidins were retained whenpretreated cocoa solids were used to prepare the binder syrup. Therewere no further losses when the binder syrup prepared with thepretreated cocoa solids was formulated into dark or milk chocolate chewsor chocolate granola bars.

Other variations and modifications, which will be obvious to thoseskilled in the art, are within the scope and teachings of theseinventions. The inventions are not to be limited except as set forth inthe following claims.

1. A process for conserving the effectiveness of a particulate, foodgrade antioxidant or antioxidant-containing particles comprises the stepof pretreating the antioxidant or the antioxidant-containing particles,prior to formulation into a food or a food supplement, with about 9% toabout 90% by weight of a food-grade oil and/or a fat having a meltingpoint below about 80° C. and optionally up to about 5% by weight anemulsifier, the weights being based on the weight of the antioxidant orthe antioxidant-containing particles.
 2. The process of claim 1, whereinthe particles are about 1 to about 150 microns, wherein the antioxidantand antioxidant-containing particles are selected from the groupconsisting of butylated hydroxyanisole, butylated hydroxytoluene,tertiary butylated hydroquinone, propyl gallate, a phenolic acid, apolyphenol, ascorbic acid, stannous chloride, a tocopherol, sulfurdioxide, and dilauryl thiodipropionate; wherein the oil and/or the fatis selected from the group consisting of cocoa butter, a polyol ester, asterol ester, a stanol ester, a triglyceride, a fatty alcohol ester of apolycarboxylic acid, an esterified alkoxylated polyol, a glycerol ester,and a vegetable oil, a partially hydrogenated vegetable oil and mixturesthereof; and wherein the emulsifier is selected from the groupconsisting of lecithin, a mono- or diglyceride, an ethoxylated mono- ordiglyceride, a phospholipid, an ester of a monoglyceride and acetic,lactic, citric, succinic, or tartaric acid, a fatty acid ester of apolyglycerol, a sorbitan ester, a sucrose ester, propylene glycol,polyglycerol polyresorcinoleate, and mixtures thereof.
 3. The process ofclaim 2, wherein the antioxidant-containing particles are mixtures ofcocoa polyphenols present in fully defatted or partially defatted cocoasolids having a particle size of about 5 to about 70 microns; andwherein the particles are pretreated with about 20% to about 40% byweight of sterol ester(s) and/or stanol ester(s).
 4. A process forconserving the effectiveness of a particulate food grade antioxidant orantioxidant-containing particles comprises the step of pretreating theantioxidant or the antioxidant-containing particles, prior toformulation into a food or a food supplement, with about 0.05% to about5% by weight of a lecithin.
 5. The process of claim 4, wherein theantioxidant-containing particles are mixture of cocoa polyphenolspresent in fully or partially defatted cocoa solids; having a particlesize of up to about 150 microns and wherein the particles are pretreatedwith about 0.03% to about 0.1% of soy lecithin.
 6. An additive for afood or a food supplement comprising partially or fully defatted cocoasolids pretreated by mixing with about 9% to about 90% by weight, basedon the cocoa solids, of sterol ester(s) and/or stanol ester(s) which areliquids at temperatures of about 80° C. or less, wherein the cocoasolids after pretreatment have a cocoa procyanidin content of at leastabout 4.5 milligrams per gram of defatted cocoa solids.
 7. An additivefor a food or a food supplement comprising partially or fully defattedcocoa solids pretreated by mixing with about 0.05% to about 5% byweight, based on the cocoa solids, of a lecithin, wherein the cocoasolids prior to pretreatment have a cocoa procyanidin content of atleast about 5 milligrams per gram of defatted coca solids.
 8. A processfor preparing a binder syrup for a food or a food supplement comprisesthe step of mixing at about 20° C. to 160° C. (i) a syrup and (ii)partially or fully defatted cocoa solids pretreated by mixing with about9% to about 90% by weight, based on the cocoa solids, of sterol ester(s)and/or stanol ester(s) which are liquids at temperatures of about 80° C.or less, wherein the cocoa solids in the binder have a cocoa procyanidincontent of at least about 4.5 milligrams per gram of defatted cocoasolids.
 9. A binder syrup prepared by the process of claim
 8. 10. Abinder syrup comprising a mixture of (i) a syrup and (ii) cocoa solidsare pretreated with about 9% to about 90% by weight of sterol ester(s)and/or stanol ester(s) and optionally with up to about 5% by weight of alecithin and/or up to about 20% by weight of a chocolate liquor; whereinthe binder syrup is liquid at about 40° C. to 80° C. and solid at roomtemperature, the weights being based on the cocoa solids.
 11. A processfor preparing a dry, ready-to-eat food comprises the steps of: (a)pretreating cocoa solids having a cocoa procyanidin content of at leastabout 5 milligrams per gram of defatted cocoa solids with about 9% toabout 90% by weight of sterol ester(s) and/or stanol ester(s) andoptionally with up to about 20% by weight of a chocolate liquor and/orabout 0.05% to 5% by weight of an emulsifier; the weights being based onthe cocoa solids; (b) mixing the pretreated cocoa solids and a syrupwith a mixture of dry ingredients comprising grain(s), flour(s), and/orprotein(s) and optionally dried fruits and/or nuts to obtain a formablefood; and (c) forming the food; wherein the pretreated cocoa solids andthe syrup are liquid when blended into the dry ingredients and solidwhen the formed food is cooled to room temperature.
 12. The process ofclaim 11, further comprising the steps of decorating or enrobing theformed food with chocolate, a yogurt, or a flavored sugar.
 13. Theprocess of claim 11, wherein the pretreated cocoa solids and the syrupare premixed at about 60° C. to about 80° C. to form a binder syrupprior to blending with the dry ingredients.
 14. The process of claim 11,wherein the cocoa solids are partially defatted cocoa solids containingabout 8-30% fat and having a cocoa procyanidin content of at least about50 to about 150 milligrams; wherein the sterol ester(s) are preparedfrom rapeseed oil; wherein the emulsifier is selected from the groupconsisting of lecithin, a monoglyceride, a diglyceride, an ethoxylatedmono- or diglyceride, a phospholipid, an acetic, lactic, citric,succinic, or diacetyl tartaric acid ester of a monoglyceride, apolyglycerol, sorbitan, a sucrose ester, or a propylene glycol ester ofa fatty acid, polyglycerol polyresorcinoleate, and mixtures thereof;wherein the syrup further comprises an ingredient selected from thegroup consisting of a whole milk powder, a skim milk powder, a maltedmilk powder, a flavorant, one or more vitamins or minerals, a sugar, asalt, and mixtures thereof; and wherein the dry ingredients are selectedfrom the group consisting of rice crisps, soy crisps, oats, bran flour,corn flour, wheat flour, rice flour, a milk protein, an egg protein, asoy protein, a whey, and combinations thereof.
 15. The process of claim14, wherein the cocoa solids have a cocoa procyanidin content of about50 to 80 milligrams; wherein the sterol ester(s) comprise ester ofβ-sitosterol, campesterol, and stigmesterol; wherein the emulsifier islecithin; wherein the flavorant is vanilla; wherein the syrup is cornsyrup having a DE of about 40 to about 65; and wherein the sugar is abrown sugar and/or fructose, and wherein the dry ingredients compriserice crisps, soy crisps, and/or oats.
 16. A dry, ready to eat granolabar prepared by the process of claim
 15. 17. The bar of claim 16, whichcontains about 65% to 100% of the cocoa procyanidins present in thecocoa solids.
 18. The bar of claim 17, which contains about 90% to 100%of the cocoa procyanidins.
 19. A dry, ready to eat health bar containingsterol ester(s) and/or stanol ester(s) and at least about 2 milligramsof cocoa procyanidins per gram of the bar.
 20. A process for preparing achocolate confectionery comprises the steps of: (a) pretreating cocoasolids having a cocoa procyanidin content of at least about 5 milligramsper gram of defatted cocoa solids with about 9 to about 90% of sterolester(s) and/or stanol ester(s) and optionally up to about 20% ofchocolate liquor and/or about 0.5% to about 5% of an emulsifier; (b)blending the pretreated cocoa solids with a syrup at about 20 C to about160 C; (d) cooling the blend; and (e) shaping the cooled blend into theconfectionery.
 21. The process of claim 20, wherein the cocoa solidshave a fat content of about 8% to about 30% and a cocoa procyanidincontent of about 50 to about 150 mg; wherein the sterol ester(s) areprepared from rapeseed oil; wherein the emulsifier is selected from thegroup consisting of lecithin, a monoglyceride, a diglyceride, anethoxylated mono- or diglyceride, a phospholipid, an acetic, lactic,citric, succinic, or diacetyl tartaric acid ester of a monoglyceride, apolyglycerol, sorbitan, a sucrose ester, a propylene glycol ester of afatty acid, polyglycerol polyresorcinoleate, and mixtures thereof;wherein the chocolate liquor is a dark chocolate liquor of a milkchocolate liquor present in an amount of about 0.5% to about 10%; andwherein the syrup is an aqueous solution of a nutritive carbohydratesweetener or an artificial sweetener having a moisture content of about5 to about 25%; and wherein the syrup further comprises a gum,vitamin(s) and/or mineral(s), a sugar, and/or a flavorant.
 22. Theprocess of claim 21, wherein the sterol esters, the chocolate liquor,and the lecithin are premixed before mixing with the cocoa solids; andwherein the syrup is a corn syrup having a DE of about 40 to about 65.23. A dark chocolate or milk chocolate chew prepared by the process ofclaim
 22. 24. The chew of claim 23, which contains about 65% to 100% ofthe cocoa procyanidins present in the cocoa solids.
 25. The chew ofclaim 24, which contains about 90% to 100% of the cocoa procyanidins.26. A dark or milk chocolate chew containing sterol ester(s) and/or astanol ester(s) and at least about 2 milligrams of cocoa procyanidinsper gram of the chew.